Ternary synergistic sudsing detergent compositions



y 1967 T. 1.. COWAFQD ETAL 3,332,879

TERNARY SYNERGISTIC SUDSING DETERGENT COMPOSITIONS Filed Dec. 5, 1966 GRAPH SHOWlNG SUDSING SYNERGISM I lOO/ DeTergent (I) Bdsic Formulufion (Weight Basis) 11 |OO% Detergeni (H) 30% Total Acrive m IOO% Detergent (III) Q 8% EihyL Alcohol 62% Water INVENTORS Todd'L. Coward Curl Barker United States Patent 3,332,879 TERNARY SYNERGISTIC SUDSING DETERGENT COMPOSITIONS Todd L. Coward, Cincinnati, and Carl Barker, Blue Ash,

Ohio, assignors to The Procter & Gamble Company,

Cincinnati, Ohio, a corporation of Ohio Filed Dec. 5, 1966, Ser. No. 599,205 13 Claims. (Cl. 252152) ABSTRACT OF THE DISCLOSURE A detergent composition having synergistic sudsing properties consisting essentially of a ternary mixture of from about 25% to about 80% by Weight of Detergent I which is a sulfonated detergent as described in the summary of this invention; from about to about 50% by weight of Detergent II which is an alkyl glyceryl ether sulfonate detergent, and from about 5% to about 40% by weight of Detergent III which is a fatty acid amide detergent.

BACKGROUND OF THE INVENTION 1. Field of the Invention The detergent compositions of the present invention consisting essentially of a synergistic mixture of three detergents find wide application in any washing and cleaning situation. It can be formulated, for example, into unbuilt light-duty detergent compositions and medium-duty and heavy-duty built detergent compositions. These terms as understood in the art connote the intended use of a detergent composition. They suggest that additional ingredients can also be present in complete detergent formulations to improve certain performance characteristics or desired properties of the final composition. The term lightduty applies to detergent compositions intended for use under mild conditions of handwashing lightly-soiled garments and delicate fabrics in cool or warm water. Such compositions are mainly comprised of the active detergent ingredients and little or no additional compounds such as detergency builders and other cleaning aids. The term heavy-duty describes just the opposite of light-duty, and suggests stronger, more fortified characteristics. Thus, for example, heavy-duty implies machine washing of heavily soiled clothes or garments with hot water and vigorous agitation. Heavy-duty formulations contain proportionately large amounts of cleaning additives such as detergency builders, alkaline compounds as pH adjusters, and many others which contribute to the expected overall performance requirements of a diflicult cleaning situation. The term medium-duty describes detergent compositions whose formulations are intermediate lightand heavy-duty formulations to afford flexibility of detergent products to meet and satisfy any cleaning or washing requirements.

Light-, mediumand heavy-duty detergent compositions can be in any physical form including liquids and solids. The synergistic ternary detergent mixture of the present invention can be formulated into any of the usual forms including liquids, granules and powders, flakes, tablets and the like.

DESCRIPTION OF THE PRIOR ART The prior art has long sought detergent compositions which have improved properties such as improved mildness, increased sudsing and better cleaning, among other features. At times it is particularly desirable to provide detergent compositions having markedly improved sudsing properties. In dishwashing situations, for instance, especially in household applications, it is generally re- ICC garded as desirable to have a suds blanket cover the washing solution during the full period that dishes are being washed. Presence of suds in such applications is regarded by housewives as an indication of the cleaning power of the Washing solution. Likewise, the presence of copious amounts of suds in laundering situations is used by many as an indicator of the cleaning power of a given washing formulation. It is a primary object of this invention to provide a detergent composition which has synergistic sudsing properties and which has wide application in detergent products.

Improved performance charactertistics due to unobvi? ous synergistic results are described in US. Patent 3,223,- 647 (mildness properties), US. Patent 2,383,737 (cleaning power), and copending patent application Serial No. 524,364, filed Dec. 23, 1965.

SUMMARY OF THE INVENTION A detergent composition of the present invention having synergistic sudsing properties is a mixture of three detergents which mixture consists essentially of (I) From about 25% to about of Detergent I which comprises from about 30% to about 70% of Component A, from about 20% to about 70% of Component B and from about 2% to about 15% of Component C,

wherein:

(a) said Component A is a mixture of double-bond positional isomers of water-soluble salts of alkenel-sulfonic acids containing from about 12 to about 16 carbon atoms, said mixture of positional isomers including by Weight about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a beta-gamma unsaturated isomer, about 5% to about 25% of a gamma-delta unsaturated isomer, and about 5% to'about 10% of a deltaepsilon unsaturated isomer;

(b) said Component B is a mixture of Water-soluble salts of bifunctionally-substituted sulfur containing saturated aliphatic compounds containing from about 12 to about 16 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atom, at least of said component having hydroxyl radicals attached to the third, fourth, or fifth carbon atoms;

(c) said Component C is a mixture comprising from 30-95% water-soluble salts of alkene disulfonates containing from about 12 to about 16 carbon atoms, and from about 5% to about 70% water-soluble salts of hydroxy disulfonates containing from about 12 to about 16 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group;

(II) From about 5% to about 50% of Detergent II Which is an alkyl glyceryl ether sulfonate detergent having a straight chain alkyl group of from about 10 to about 14 carbon atoms, the cation of said sulfonate being selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, ammonium, sodium, and potassium and mixtures thereof; and

(III) From about 5% to about 40% of Detergent III which is a fatty acid amide selected from the group consisting of fatty acid monoethanolamide, fatty acid monoisopropanolamide, and fatty acid glycerylamide, the fatty acid groups containing to 14 carbon atoms.

Detergent 1 According to the present invention, Detergent I is itself a mixture of certain compounds containing from 12 to 16 carbon atoms, preferably 14 carbon atoms. As noted above, it is basically a mixture of three components each of which has a specific composition and each of which contains compounds containing from 12 to 16 carbon atoms. A detailed discussion of Detergent I is presented below.

A preferred percentage range by weight for Component A is from about 35% to about 65%, for Component B it is from about 25% to about 60%, and for Component C it is from about 3% to about 12%.

Component A is comprises essentially of the prescribed ranges of the following C C compounds.

In the preceding formulas x is an interger in the range from about 6 to about 10 and large enough to provide from 12 to 16 carbon atoms in the molecule. Preferably x is 8 in order to provide a molecule having 14 carbon atoms. M represents any cation that forms a watersoluble salt such as alkali metals, e.g., sodium and potassium, and ammonium, and substituted ammonium compounds, e.g., trialkylammonium and trialkylolammonium compounds. Specific examples of substituted ammonium compounds are triethylammonium, trimethylammonium, and triethanolammonium. Others will be apparent to those skilled in the art. The symbols x and M have the same meaning throughout this description of the present invention. There can also be present minor amounts of other double-bond positional isomers. This is the case, for example, when the composition is prepared by the sulfonation of alpha olefins with uncomplexed sulfur trioxide. Such minor amounts, i.e., less than about 10% by weight, do not materially alter the excellent detergent properties of the composition.

Whereas, Component A is a blend or mixture of certain C -C unsaturated isomeric aliphatic compounds, Component B consists of a mixture of certain C C saturated aliphatic compounds. A minor amount of unsaturation can be included in this mixture but preponderantly the compounds are saturated. Bifunctionality of these alkane compounds is due to the presence of a hydroxyl group and a sulfonate radical on the same molecule. It has been discovered that the sulfonate radical must be located on the terminal carbon atom. It also has been discovered that the situs of the hydroxyl group is an especially important factor in the compounds that comprise Component B. For example, if the hydroxyl group and the sulfonate radical are attached to adjacent carbon atoms, the valuable detergent properties of the Component -B compounds are substantially decreased. This is especially true when the alpha and beta carbons are the two sites of attachment. The critical structural arrangement which must exist in order for the compounds to be detergents, is that the sulfonate radical must be in the alpha position and the hydroxyl radical Permis- Presible ferred Range, Range. Percent Percent CH3(CH2)XCH2CHzCH(OH) OH2CH2SO3M 10 25-75 CHa(CHz)XCI-I2CH(OH)CH2CH2CHzSOsM 10*90 25-75 OHs(CHz)xOI-I(OH)OH CH CHzCHzSOaM... 10-90 25-75 The value of x and M are as previously set forth.

Component B can also include minor quantities, for example, less than about 10% of compounds wherein the hydroxyl group is attached elsewhere along the carbon chain, e.g., on the sixth carbon atom, without materially altering the overall detergent properties of the compositions. The 3-, 4-, and S-hydroxy n-alkyl sulfonate compounds, illustrated above, are preferred ingredients in Component B and they should constitute at least about 90% by weight thereof.

In this same connection, it has also been noted that corresponding beta-hydroxy n-alkyl sulfonate compounds are relatively poor detergent compounds. Not only are they comparatively poor detergents, but it has been discovered also that such compounds constitute an actual load on the present detergency system. For this reason, the level of such compounds should be held to a minimum. It is noted though, that minor amounts of betahydroxy n-alkyl sulfonate compounds can be tolerated in the synergistic compositions of this invention provided that Components A, B and C of Detergent I otherwise contain the essential ingredients herein described in the proportions and percentages specified.

The alkene disulfonates should preferably comprise from about 40% to about 80% of the highly polar polyfunctionally substituted C -C aliphatic compounds which make up Component C. These alkene disulfonates should also contain about 12 to about 16 carbon atoms and, preferably, 14 carbon atoms. As seen above, one sulfonate group is attached to the terminal carbon atom. The second sulfonate group is attached to an internal carbon atom that is not more than about six carbon atoms removed from the terminal carbon. In other words, the second sulfonate functional group can be attached to the second through about the seventh carbon atom. Component C can also include minor amounts of compounds in which the second sulfonate is located more internally than the seventh .carbon, such as, for example, on the eighth carbon, etc. There is no apparent advantage in having these latter compounds present in the composition, however. According to a preferred embodiment, the major portion, that is from about 60% to about of the alkene disulfonates, should be 1.2 and 1.3 disulfonates.

The alkene double bond can be distributed between the terminal carbon and about the seventh carbon atom; such unsaturation includes, for instance, alpha-beta, beta-gamma, gamma-delta, delta epsilon, epsilon-zeta, and zeta-eta unsaturation. Preferably, the double bond should be distributed between the second to the sixth carbon atom. It should be noted that the alkene double bond can be even more internally located than between the zeta-eta carbons, but again no apparent advantage is gained thereby.

Thus, it can be seen that the alkene disulfonates of Component C contain the polyfunctional combination of a double bond and two sulfonate groups in an important structural relationship. The preferred compounds as ingredients of the alkene disulfonate portion of Component C are 2-alkene-1,2-disulfonate; 3-alkene-1,2-disulfonate; and 4-alkene-1,2-disulfonate of the 1,2-disulfonate species; and 3-alkene-1,3-disulfonate; 4-alkene-1,3-disul fonate; and 5-alkene-1,3-disulfonate of the 1,3 disulfonate species. The alkene group can contain from about 12 to about 16 carbon atoms and preferably about 14 to 16 carbon atoms. The sodium and potassium salts of these compounds are preferred.

Examples of alkene disulfonate compounds are the following in which a carbon chain length of 14 is selected as being illustrative, having sulfonate attachment sites of 1,2 and 1,3;

"16 carbon atoms. The terminal carbon atom has attached to it one of the sulfonate groups. The second sulfonate group can be attached to an internal carbon atom not more than six carbon atoms removed from said terminal carbon atom. The required hydroxy group is attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group.

The preferred sites of attachment for the hydroxy group on the 1,2 disulfonate species are the fourth and fifth carbon atoms to yield 4-hydroxyalkane-1,2-disulfonates and S-hydroxyalkane-1,2-disu1fonates. For the 1,3 disulfonates the preferred sites of attachment for the hydroxy group are the fifth and the sixth carbon atoms to yield S-hydroxyalkane-1,3-disulfonates and 6-hydroxyalkane-1,3-disulfonates. The alkane hydrocarbons as before are those having 12 to 16 carbon atoms and preferably 14. According to a preferred embodiment, the major portion, that is, from about 60% to about 95% of the hydroxy disulfonates should be 1,2 and 1,3 disulfonates.

Thus, for example, the following compounds are contemplated. Again, a 14 carbon 1,2 and 1,3 disulfonate compound is presented as being representative.

It is postulated that a second polar group, as in Components B and C, spaced a critical distance from a terminally attached polar group in a detergent molecule modifies the crystalline la'tice structure in such a way as to improve markedly the solubility characteristics of the compound. While this is not known for certain, it is offered as one possible explanation for the exceptional detergent properties of the compositions of the present invention.

Detergent I as described herein can be prepared in any suitable manner so long as the above teachings are adhered to. For instance, each of the ingredients can be synthesized separately and then mixed according to the stated proportions. On the other hand, it is possible to prepare Detergent I of the present invention according to a novel process described in copending patent application Ser. No. 561,352, filed June 29, 1966, by Adriaan Kessler and Phillip F. Pfiaumer.

If it is desired to synthesize separately the individual components of Detergent I, it is possible to do so according to the procedures in the following discussion. Any other suitable methods can be used. The symbol R as used in the following equation represents an aliphatic hydrocarbon radical that would allow for a total of carbon atoms in the molecule between about 12 and about 16. The alpha-beta unsaturated sulfonate containing aliphatic compounds of Component A can be prepared readily by dehydrochlorinating a Z-chIorosulfonic acid derivative. A fairly detailed discussion of a suitable preparative route appears in an article in the Journal of the Chemical Society, 1949, page 46, written by J. D. Rose and A. Lambert. The starting step for this synthesis is a reaction between a long chain epoxide and sodium bisulfite to produce a Z-hydroxy-l-sulfonate derivative of the particular long chain epoxide used. This reaction pro-duct is condensed with PCl to prepare the aforementioned 2-chlorosulfonic acid derivative which in turn is reacted with sodium carbonate to yield an alpha-beta unsaturated compound.

The other preferred double-bond positional isomers of Component A, i.e., the beta-gamma, gamma-delta, and delta-epsilon can be prepared by the thermal dehydration of hydroxysulfonates. According to the following reaction, the thermal dehydration of the sodium salt of 3-hydroxysulfonate results in the preparation of a reaction mixture containing the beta-gamma isomer and the gamma-delta isomer.

ROH2OH=OHCH2SOaNa RCH CHGHzCH SOgNt! Similarily a reaction mixture of a gamma-delta and a delta-epislon double-bond isomer compound can be prepared by using a 4-hydroxysulfonate as a starting material:

The foregoing synthesis of the double-bond positional isomers follows closely the well known dehydration of an organic alcohol as is mentioned in such standard texts as Whitmores Organic Chemistry, second edition, pages 3941.

There is no need to separate the reaction product of the two illustrated dehydration reaction. The reaction product can be formulated directly into a detergent composition according to the present invention. If, for some reason, it is desired to work with pure ingredients, they can be separated into pure forms.

The hydroxy sulfonates of Component B, such as the preferred 3-, 4-, and 5-hydroxy compounds can be prepared by the free radical addition of sodium bisulfite to the corresponding 3-, 4-, or S-hydroxy-l-olefin, respectively:

Free Radical Catalyst RCH(OH)CH=CH2 NaHSO;

ROH(OH) OHzCHzSOaNa sodium 3-hydroxyalkane sulfonate The hydroxy olefin for use as starting materials in the preceding free radical addition reaction can be prepared by well known organo-metallic reactions, e.g., involving an aldehyde and a Grignard reagent in which R and R are organic radicals and X is a halogen. For example:

sodium 4-hydr0xyalkane sulfonate A discussion of the conversion of hydroxyolefins produced by preceding Equations a and b to hydroxy sulfonates appears in an article written by J. Willens, Bulletin of the Chemical Society of Belgium, vol. 64, page 427 (1955).

It is to be understood that other hydroxy sulfonates as desired can be prepared by using different Grignard reagents in the reaction equation set forth above.

The alkene disulfonates and the hydroxy disulfonates which comprise Component C may also be prepared separately by any known manner. For instance, the hydroxy disulfonates may be prepared by epoxidizing olefin sulfonic acid isomers, and then opening the epoxide ring with sodium bisulfite by standard reaction techniques. The hydroxy disulfonates may then be dehydrated by reactions known to those skilled in the art to yield the corresponding isomeric alkene disulfonates.

As mentioned earlier, the Detergent I components should contain from about 12 to about 16 carbon atoms. In its p-referred embodiment, Detergent I should consist of compounds containing 14 carbon atoms or compounds in the 12 to 16 carbon range but averaging 14 carbon atoms. It is not necessary that each of the compounds contain the same number of carbon atoms. Mixtures of different chain lengths within the prescribed ranges can be used.

For example, a Detergent I composition can be prepared by independently treating alpha olefin raw materials containing 12, 14 and 16 carbon atoms by the procedure described in copending patent application Ser. No. 561,352, filed June 29, 1966, by Kessler and Pfiaumer, then mixing the portions of the resulting sulfonated products, e.g., 30% C 40% C 30% C or as another example, 10% C C 10% C or another example, 1s mixing equal weight mixtures of C C and C compounds having the compositions described above.

Alternatively, a mixture of alpha olefins containing 12, 14 and 16 carbon atoms can be treated according to the procedure described in copending patent application Ser. No. 561,352, filed June 29, 1966, by Kessler and Pflaumer.

The following compositions are illustrative of the make up of Detergent I according to the present inventron wherein the percentages are by Weight and wherein Components A, B and C total up to of Detergent I. The percentages listed for each ingredient are by weight of that particular ingredient in Detergent I.

Detergent I can be comprised as follows with a chain length of 14 carbons being representative:

CH CHgSO NB. .5

Total Component C 10 This Detergent I composition listed above has excellent detergent and synergistic sudsing properties when mixed with Detergents II and III according to the proportions described herein.

Another illustrative example of Detergent I is as follows: (C being represented) Component A: Percent C H CH=CHSO Na 9 cnHggcH cHcHgsogNa C H CH=CHCH CH SO N21 C H CII CHCHgCHgCHgSOgNQ.

Total Component A 65 Component B: Percent C11H23CH(OII) CHzCHgSOgNH. C H CH(OH)CH CH CI-1 SO Na 10 CHzCHzCHzCHgSOgNZ. 3

Total Component B 23 z r O UIUIUIOLIIO This Detergent I composition also offers excellent detergent properties of cleaning and synergistic sudsing in admixture with Detergents II and III as described herein.

Detergent II Detergent II is an alkyl glyceryl ether sulfonate detergent having a straight chain alkyl group of from about to about 14 carbon atoms, the cation of said sulfonate being selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, ammonium, sodium, and potassium, and mixtures thereof. Preferably, the alkyl group should contain 12 carbon atoms or be comprised of mixtures of chain lengths averaging 12 carbon atoms. One preferred embodiment is having the alkyl group being derived from coconut alcohol and especially the middle-cut coconut alcohol containing 2% C 66% C 23% C and 9% C The preferred compound is referred to hereinafter as CnAGS.

Other illustrative examples besides sodium CnAGS are sodium decyl glyceryl ether sulfonate, sodium dodecyl glyceryl ether sulfonate, sodium tetradecyl glyceryl ether sulfonate, and the corresponding potassium salts. Mixtures of such compounds can also be used. The alkyl group can be obtained from synthetic as well as natural sources, e.g., coconut alcohols, and the like.

Detergent III Detergent III is a fatty acid amide selected from the group consisting of fatty acid monoethanolamide, fatty acid monoisopropanolamide, and fatty acid glycerylamide. Mixtures of these compounds can also be used.

The fatty acid group should contain fro-m 10 to 14 carbon atoms and be obtained from natural or synthetic sources. Preferably, the fatty acid group should contain 12 carbon atoms, or if compounds having mixed chain lengths are used, they should contain an average of 12 carbon atoms. An example of the latter is a coconut alkyl group obtained from the middle-cut of distilled coconut fatty acid which consists of a mixture of various chain lengths being approximately 2% C 66% C 23% C14, and C16.

Other examples are decyl monoethanolamide, dodecyl monoethanolamide, and tetradecyl monoethanolamide. The corresponding chain lengths of isopropanolamide and glycerylamide are also useful, as are mixtures of these compounds.

The preferred compound is coconut monoethanolamide, the coconut alkyl group having the composition noted above.

The synergistically improved sudsing performance of the novel ternary detergent compositions of the present invention was discovered by preparing liquid detergent compositions containing each of the three different detergent compounds as sole cleaning agents and also representative mixtures of such detergent compounds. The compositions were standardized to include a total of 30% by weight of an active detergent ingredient, 8% of an ethyl alcohol solubilizer with the balance, 62%, being water.

Each of the detergents was first tested separately and then in certain prescribed mixtures with each other.

The specific testing procedure designed to evaluate these several detergent compositions is now described. A dishpan was prepared containing one gallon of water with a hardness of 7 grains, a temperature of F. and a pH of 7. To this was added 7.25 cc. of each of the detergent compositions being tested. The washing solution containing the detergent composition was mechanically agitated to produce the maximum suds level which was measured. This is referred to as the original suds level. Agitation was by means of a mechanical stirrer.

After this original suds level was obtained, a series of five ordinary dinner plates each soiled with about 2 grams of standardized fatty soil (a triglyceride shortening) were washed in the prepared test solution. The suds height was again measured. This procedure was repeated 2. fixed number of times with a suds height measurement being taken after each set of five dishes were washed. An average was then calculated for the several suds height measurements, and the average was then expressed in terms of a percentage of the original suds height. This percentage figure is regarded as a relative measure of two important areas of suds performance, namely, initial suds volume and even more important, suds stability in the presence of increasing soil load. The results are highly dependable and reproducible. Those skilled in performing this evaluation know from experience that a difference in suds height of from about 3% to about 5% is considered statistically significant.

The results of these evaluations are presented graphically in the attached drawing.

BRIEF DESCRIPTION OF THE DRAWING The drawing is a triangular graph of the sudsing results obtained with Detergent I, Detergent II, and Detergent III and mixtures thereof. On this triangular graph, I at the top of the triangle represents Detergent I used as the sole active in the test formulation.

In these examples, Detergent I consisted of a 30% C 40% C and 30% C mixture.

The C material had the following composition:

Component A: Percent C1 HQ1CH CHSO3Na CQH1QCHZCHCHZSO3NB. CgH1'7cH CHCH2CH2SO3Na C H CH- CHCH CH CH SO Na 6 Total Component A 65 Component B: Percent C H CH(OH)CH CH CH SO Na 5 Total Component B 25 Component C: Percent C H CH CHcH(SO Na)CH (SO Na) 4.5 C H CH CHCH(SO Na) CH CH (SO Na) 1.5

(SO Na) 3.0 C H CH(OH)CH CH(SO Na)CH CH (SO Na) 1.0

Total Component C 10 The C had the following composition:

Component A: Percent C H CH=CHSO Na 13 C11H23CH CHCH2SO3Na C H CH CHCH CH SO Na C H CH=CHCH CH CH SO Na 6 Total Component A 65 1 1 Component B Percent C H CH (OH CH CH SO Na 20 C10H21CH(0H) CH CH CH SO Na 5 Total Component B 25 Component C: Percent C H CH=CHCH(SO Na)CH (SO Na) 4.5

S03N3.) CH2CH2 SO Na) 1.5 C10H21CH(OH) CH2 (SO Na) 3 .0 C9H19CH (SO Na) 1.0

Total Component C 10 The C material had the following composition:

Component A: Percent C H CH=CHSO Na C H CH=CHCH SO Na 3 3 C 2H25CH CHCH2CH2SO3Na C11H23CH cHcH2CH2CH2SO Na 6 Total Component A 65 Component B Percent C H CH(OH)CH CH SO Na C H CH (OH) CH CH CH SO Na 5 Total Component B 25 Component C: Percent C H CH=CHCH (SO Na) CH SO Na) 4.5 C H CH CHCH (SO Na) CH CH (SO Na) 1.5 C H CH(OH) CH CH(SO Na)CH (SO Na) 3 .0 C H CH( OH) CH CH(SO Na)CH CH (SO Na) 1 .0

Total Component C 10 Detergent II in the drawing was coconut alkyl glyceryl ether sulfonate as described above (CnAGS).

Detergent III in the drawing was coconut monoethanolamide as described above (CnMEA).

From the drawing it can be seen that synergistic sudsing results are obtained with ternary mixtures consisting of 25% to 80% Detergent I, 5% to 50% Detergent II, and 5% to 40% Detergent III. Ternary compositions falling within this area on the triangular graph afiord suds percentages as defined above in excess of about 50%. This represents an exceptionally large amount of stable suds and was an unexpected discovery. To fully appreciate the magnitude of this synergism, it can be seen that Detergent Ithe C C C mixture alone provides a percentage of less than 45 Detergent IICnAGS alone also provides a percentage of less than 45%, whereas Detergent IIICnMEA provides a percentage of less than 35 As respects binary mixtures of these detergents, Detergent I and Detergent II mixtures and Detergent I and Detergent III mixtures provided less than 50% but slightly more than 45 Such results themselves represent unobvious synergistic performance and indeed form the basis for copending patent application, Serial No. 515; 826, filed December 23, 1965. By the same token, the best results achieved with a binary mixture of Detergent II and Detergent III were more than 40% but less than 45%.

The percentage lines in the drawing were drawn by joining all of the common points plotted which provided 5 0% of the original suds height, 45% of the original suds height, 40% of the original suds height and 35 of the original suds height. Ternary compositions coming within the area enclosed by the 50% line provide the synergistic sudsing results described herein.

12 CONTINUATION OF SUMMARY OF INVENTION The detergent composition of this invention consisting of the synergistic ternary mixture described above can be used in built or unbuilt formulations. Such formula tions can be liquid or solid compositions. Liquid detergent compositions have found wide acceptance especially for light-duty applications such as handwashing of dishes, fine fabrics, woolens, and lightly soiled garments.

Light-duty unbuilt liquid detergent compositions of the present invention can contain from about 5% to about 50% of the synergistic ternary mixture of Detergents I, II and III, the balance being from about 50% to about 95% water, and from about 0% to about 30% of a solubilizing agent selected from the group consisting of methyl alcohol, ethyl alcohol, propyl alcohol and isopropyl alcohol.

Preferably, however, the detergent synergistic mixtures can range from about 10% to about 35% by weight of the composition, from about 65% to about water, and from about 2% to about 15% of the solubiliz-ing agent.

A specially valuable embodiment of the present invention is a built detergent composition consisting essentially of a detergent and a builder in which the detergent is a synergistic ternary mixture of Detergent I. Deter-gent II and Detergent III and the builder is selected from the group consisting of a water-soluble inorganic alkaline builder, a water-soluble organic alkaline sequestering builder, or mixures thereof, the proportion by Weight of said detergent to said builder being in the range of from about 10:1 to about 1:10 and preferably from about 5:1 'to about 1:5.

Water-soluble inorganic alkaline builder salts which can be used alone or in admixture are alkali metal carbonates, 'borates, phosphates, polyphosphates, bicarbon ates and silicates. Specific examples of such salts are sodium and potassium, tripolyphosphate, sodium and potassium carbonate, sodium and potassium tetraborate, sodium and potassium pyrophosphate, sodium bicarbonate, sodium hexametaphosphate, sodium sesquicarbonate, sodium monoand di-ortho phosphate and potassium bicarbonate. Such inorganic builder salts enhance the overall cleaning characteristic of the novel synergistic mixtures of the present invention. Generally the potassium salts of these compounds are preferred for reasons of solubility. Potassium pyrophosphate is the single preferred builder for use in the present invention.

Examples of organic alkaline builder salts which can be used alone or in admixture are alkali metal, ammonium or substituted ammonium, vaminopolycarboxylates, e.-g., sodium and potassium N-(2-hydroxyethyl)-ethylenediaminetriacetates, sodium and potassium nitrilotr-iacetates and sodium, potassium and trie-thanolammonium-N-(2-hydroxyethyl)-nitrilodiacetates. Mixed salts of these polycarboxylates are also suitable. Other valuable polycarboxylate builder compounds are the sodium and potassium salts of polymaleate, polyitaconate, and polyacrylate. The alkali metal salts of phytic acid, e.g., sodium phytate, are also suitable as organic alkaline builder salts (see US. Patent 2,739,942).

Polyphosphonates are also valuable builders in terms of the present invention including specifically sodium and potassium salts of ethane-l-hydroxy-l,l-diphosphonate, sodium and potassium salts of methylene diphosphonate, sodium and potassium salts of ethylene diphosphonate, and sodiumand potassium salts of ethane-1,1,2-triphosphonate. Other examples include the alkali metal salts of ethane-Z-carboxy-1,1-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-lhydroxy-l,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2- triphosphonic acid, propane-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3-tetraphosphonic acid, and propane-1,22,3- tetraphosphonic acid.

The built detergent compositions prepared according to the present invention are preferably used in an aqueous 13 solution having a pH within a range of about 9 to about 12 and preferably between 10 and 11.5.

A built liquid detergent composition prepared according to this invention contains from about to about 50% by weight, preferably 8% to 40%, of a synergistic ter- 5 invention.

TAB LE I Examples III VI VII VIII IX DETERGENT I (a) Cn-sulionated detergent described above (b) Cn-sulfonated detergent described above (0) Cit-sulionated detergent described above (d) 30% C12, 40% C14, 30% C sulfonated detergent described above (e) O 80% C14, 10% C sulfonated detergent described above DETERGENT n (a) Sodium OnAGS (b) Sodium decyl glyceryl ether sulfonate.

(0) Sodium dodecyl glyceryl ether sulfonate- ((1) Sodium tetradecyl glyceryl ether sulfonate DETERGENT In (a) Coconutmonoethanolamide (b) Decylmonothanolamide. (c) Dodecylmonoethanolamide.

(d) Tetradecylmouoethanolami (e) Cdconutisopropanolamide. (f) Coconutglycerylamide nary detergent mixture described herein, from about 4% to about by weight, preferably about 8% to about 25%, of a detergency builder selected from the group consisting of water-soluble inorganic alkaline builders, water-soluble organic alkaline sequestering builders, and mixtures thereof, and the balance to 100% water.

Hydrotropes can be added if desired to increase the compatibility of the ingredients of the formulations of this invention. Preferred hydrotrope anions are benzene sulfonate, xylene sulfonate, and toluene sulfonate. They are preferably used as their soluble salts such as: ethanolammonium, diethanolammonium, and triethanolammoniu-rn, and especially as the alkali metal, potassium, or sodium salts. Sodium or potassium toluene sulfonate is especially preferred. The hydrotrope is added at levels of from about 0% to about 10% by weight of the composition. Levels of from about 2% to 8% are preferred. The upper limit of about 10% is set by increasing dilution of the product by an ingredient substantially inert so far as sudsing and detergency are concerned. The lower limit is the amount required to achieve a homogeneous solution. It will be appreciated that it is necessary that the formulations of this invention should be liquid at somewhat higher and at somewhat lower temperatures than usual room temperature. The amount of hydrotrope salt used is preferably the minimum amount which will hold the ingredients in solution at the temperature to which it is desired that the formula can be cooled without phase separation.

Solubilizing agents also can be added, if necessary, and those preferred are lower alcohols such as methyl, ethyl and propyl alcohols. They are generally employed at a level of from about 0% to about 25% by Weight of the composition and preferably between about 5% to 15% by weight.

As hereinbefore mentioned, various minor ingredients can also be added to the compositions of the present invention. Such normal and desirable additives include perfumes, viscosity central agents, opacifiers, and pigments. In addition, inert materials such as water soluble inorganic salts can also be present in minor amounts, generally as impurities from the various ingredients or as opacifier stabilizers. For example, ethylene glycol distearate or poly- EXAMPLE XI Liquid detergent (unbuilt) 15% C -sulfonated detergent described above 5% Sodium coconut alkyl glyceryl ether sulfonate 4% Coconut monoethanolamide 6% Ethyl alcohol Water.

EXAMPLE XII Liquid detergent (unbuilt) 16% C -sulfonated detergent described above 8% Sodium dodecylglyceryl ether sulfonate 8% Coconut isopropanolamide 8% Isopropyl alcohol 60% Water.

EXAMPLE XIII Liquid detergent (built) 10% C -sulfonated detergent described above 2.5% Sodium coconut alkyl glyceryl ether sulfonate 2.5% Coconut monoethanolamide 25% Potassium pyrophosphate 50% Water 10% Potassium toluene sulfonate.

EXAMPLE XIV Liquid detergent (built) 12% C -sulfonated detergent described above 3% Sodium coconut alkyl glyceryl ether sulfonate 3% Coconut monoisopropanolarnide 20% Tripotassium ethane-l-hydroxy-l,l-diphosphonate 8% Sodium xylene sulfonate 54% Water.

1 5 EXAMPLE xv Solid detergent (built) 8% C -s11lfonated detergent described above 6% Sodium coconut alkyl glyceryl ether sulfonate 3.5% Coconut monoethanolamide 50% Sodium tripolyphosphate 20% Sodium sulfate 6% Sodium silicate (Na O:SiO =1:6) 6.5% Water.

EXAMPLE XVI Solid detergent (built) 15% C -sulfonated detergent described above 5% Sodium coconut alkyl glyceryl ether sulfonate 5% Coconut monoethanolamide 15% Sodium tripolyphosphate 15% Sodium ethane-1-hydroxy-l,l-diphosphonate 15 Sodium nitrilotriacetate 15% Sodium sulfate 5% Sodium silicate (Na O:SiO =2:1)

% Water.

DESCRIPTION OF PREFERRED EMBODIMENTS The preferred Detergent I, the sulfonated detergent, is one whose Components A, B, and C consist of compounds having 14 carbon atoms, or averaging 14 carbon atoms.

The preferred Detergent II, the alkylglycerylether sulfonate detergent, is coconut alkylglycerylether sulfonate or one whose alkyl group contains 12 carbon atoms, or averages 12 carbon atoms.

The preferred Detergent III, the fatty acid amide detergent, is coconut monoethanolamide and coconut monoisopropanolamide.

A preferred embodiment is a detergent composition having synergistic sudsing properties consisting essentially of a ternary mixture of from about 30% to 75% by weight of Detergent I; from about 10% to 40% by weight of Detergent II, and from about 15% to 30% by weight of Detergent III.

A preferred unbuilt liquid detergent composition of the present invention consists essentially of from about 10% to about 35% by weight of the composition of the synergistic detergent composition described herein, from about 65% to about 90% water and from about 2% to about 15 of a solubilizing agent.

A preferred built detergent composition of the present invention consists essentially of a detergent and a builder in which the detergent is the synergistic ternary composition described herein and the builder is selected from the group consisting of a water-soluble inorganic alkaline builder, a water-soluble organic alkaline sequestering builder, and mixtures thereof, the detergent and the builder being present in a proportion by weight of about 5:1 to about 1:5.

A preferred built liquid detergent composition contains from about 8% to about 40% by weight of a synergistic ternary detergent mixture described herein, from about 8% to about 25% of a builder selected from the group consisting of a Water-soluble inorganic alkaline builder, a water-soluble organic alkaline sequestering builder, or mixtures thereof, and the balance to 100% being water.

All percentages and proportions herein are by weight unless otherwise specified.

What is claimed is:

1. A detergent composition having synergistic sudsing properties consisting essentially of a ternary mixture of (I) from about 2 5% to about 80% of Detergent I which comprises from about 30% to about 70% of Component A, from about to about 70% of Component B and from about 2% to about 15 of Component C, wherein:

(a) said Component A is a mixture of doublebond positional isomers of water-soluble salts of alkene-l-sulfonic acids containing from about 12 to about 16 carbon atoms, said mixture of positional isomers including by weight about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a beta-gamma unsaturated isomer, about 5% to about 25 of a gamma-delta unsaturated isomer, and about 5% to about 10% of a deltaepsilon unsaturated isomer;

(b) said Component B is a mixture of watersoluble salts of bifunctionally-substituted sulfur containing saturated aliphatic compounds con taining from about 12 to about 16 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atom, at least of said component having hydroxyl radicals attached to the third, fourth, or fifth carbon atoms;

(c) said Component C is a mixture comprising from 30-95% water-soluble salts of alkene disulfonates containing from about 12 to about 16 carbon atoms, and from about 5% to about 70% water-soluble salts of hydroxy disulfonates containing from about 12 to about 16 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group;

(II) from about 5% to about 50% of Detergent II which is an alkyl glyceryl ether sulfonate detergent having a straight chain alkyl group of from about 10 to about 14 carbon atoms, the cation of said sulfonate being selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, ammonium, sodium, and potassium and mixtures thereof; and

(III) from about 5% to about 40% of Detergent III which is a fatty acid amide selected from the group consisting of fatty acid monoethanolamide, fatty acid monoisopropanolamide, and fatty acid glycerylamide, the fatty acid groups containing 10 to 14 carbon atoms.

2. A detergent composition according to claim 1 which consists essentially of from about 30% to about 75 of Detergent I,

from about 10% to about 40% of Detergent II, and

from about 15 to about 30 of Detergent III.

3. A detergent composition according to claim 1 wherein Detergent I consists of from about 35% to about 65% of Component A,

from about 25 to about 60% of Component B, and

from about 3% to about 12% of Component C.

4. A detergent composition according to claim 1 wherein Detergent I is comprised of compounds averaging 14 carbon atoms.

5. A detergent composition according to claim 1 wherein Detergent II is an alkyl glyceryl ether sulfonate in 17 which the alkyl group has an average of 12 carbon atoms.

6. A detergent composition according to claim 1 wherein Detergent III is selected from the group of coconutmonoethanolamide and coconutmonoisopropanolamide.

7. A liquid detergent composition consisting essentially of from about 5% to about 50% of the synergistic ternary mixture of claim 1, 50% to 95% water, and to about 30% of a solubilizing agent selected from the group consisting of methyl alcohol, ethyl alcohol, propyl alcohol, and isopropyl alcohol.

8. A liquid detergent composition according to claim 7 consisting essentially of from about 10% to about 35% by weight of said synergistic ternary mixture, from about 65% to about 90% Water and from about 2% to about 15% of said solubilizing agent.

9. A built detergent composition consisting essentially of a detergent and a builder in which the detergent is the ternary synergistic mixture of claim 1, and the builder is selected from the group consisting essentially of a water-soluble inorganic alkaline builder, a watersoluble organic alkaline sequestering builder, and mixtures thereof, the ratio by weight of said detergent to said builder being in the range of from about 10:1 to about 1:10.

10. A built detergent composition of claim 9 wherein the ratio by weight of said detergent to said builder is in the range of from about :1 to about 1:5.

11. A built liquid detergent composition consisting essentially of from about 5% to about 50% by Weight of the synergistic ternary composition of claim 1, from about 40% to about 30% by weight of a builder selected from the group consisting of a water-soluble, inorganic alkaline builder, a'water-soluble organic alkaline sequestering builder, and mixtures thereof, and the balance to 100% being water.

12. A built liquid detergent composition according to claim 11 which consists essentially of from about 8% to about 40% of said synergistic ternary composition, from about 8% to about 25% of said builder, and the balance to 100% being water.

13. A built liquid detergent composition of claim 11 which also contains from about 0% to about by 18 weight of a hydrotrope selected from the group consisting of the ethanolammonium, diethanolammonium, triethanolammonium, potassium, and sodium salts of henzene sulfonate, xylene sulfonate, and toluene sulfonate.

References Cited UNITED STATES PATENTS 2,061,617 11/1936 Downing 260513 2,061,618 11/1936 Downing 260-513 2,061,620 11/1936 Downing 260513 2,383,737 8/1945 Richardson et al. 252152 2,383,738 8/ 1945 Richardson et a1. 252'152 2,477,383 7/ 1949 Lewis.

3,072,618 1/1963 Turbak.

3,267,040 8/1966 Bright '2605l3 FOREIGN PATENTS 651,783 8/ 1964 Belgium.

OTHER REFERENCES Alpha-Olefin in the Surfactant Industry, J. Amer. Oil Chem. Society, November 1963, T. H. Liddicott, 631636.

Alkene Sulfonates Made by New Method, Chemical and Engineering News, Apr. 15, 1963, A. F. Turbak, pages 96-98.

The Reactions of Sulfur Trioxide and of its Adducts with Organic Compounds, Chemical Review, 62, No. 6, pages 549-589, December 1962.

Chem. Ber., 97, No. 10, 2903-13, October 1964, Higher Molecular Aliphatic Sulfonic Acids I., Z-hydroxyl-n-Alkane Sulfonic Acids, F. Puschel and Claus Kaiser.

Chem. Ber., 97, No. 10, 292633, October 1964, Higher Molecular Unsaturated Sulfonic Acids and the Hydrolysis of 1,3-A1kane Sulfones, F. Puschel and Claus Kaiser.

Chem. Ber., 98, 735-742, (1965), Higher Molecular Aliphatic Sulfonic Acids. IV. Sulfonation of Unbranched I Alpha-Olefins with S0 F. Puschel and Claus Kaiser. 

1. A DETERGENT COMPOSITION HAVING SYNERGISTIC SUDSING PROPERTIES CONSISTING ESSENTIALLY OF A TERNARY MIXTURE OF (I) FROM ABOUT 25% TO ABOUT 80% OF DETERGENT I WHICH COMPRISES FROM ABOUT 30% TO ABOUT 70% OF COMPONENT A, FROM ABOUT 20% TO ABOUT 70% OF COMPONENT B AND FROM ABOUT 2% TO ABOUT 15% OF COMPONENT C, WHEREIN; (A) SAID COMPONENT A IS A MIXTURE OF DOUBLEBOND POSITIONAL ISOMERS OF WATER-SOLUBLE SALTS OF ALKENE-1-SULFONIC ACIDS CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, SAID MIXTURE OF POSITIONAL ISOMERS INCLUDING BY WEIGHT ABOUT 10% TO ABOUT 25% OF AN ALPHA-BETA UNSATURATED ISOMER, ABOUT 30% TO ABOUT 70% OF A BETA-GAMMA UNSATURATED ISOMER, ABOUT 5% TO ABOUT 25% OF A GAMMA-DELTA UNSATURATED ISOMER, AND ABOUT 5% TO ABOUT 10% OF A DELTAEPSILON UNSATURATED ISOMER; (B) SAID COMPONENT B IS A MIXTURE OF WATERSOLUBLE SALTS OF BIFUNCTIONALLY-SUBSTITUTED SULFUR CONTAINING SATURATED ALIPHATIC COMPOUNDS CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, THE FUNCTIONAL UNITS BEING HYDROXY AND SULFONATE RADICALS WITH THE SULFONATE RADICALS ALWAYS BEING ON THE TERMINAL CARBON AND THE HYDROXYL RADICAL BEING ATTACHED TO A CARBON ATOM AT LEAST TWO CARBON ATOMS REMOVED FROM THE TERMINAL CARBON ATOM, AT LEAST 90% OF SAID COMPONENT HAVING HYDROXYL RADICALS ATTACHED TO THE THIRD, FOURTH, OR FIFTH CARBON ATOMS; (C) SAID COMPONENT C IS A MIXTURE COMPRISING FROM 30-95% WATER-SOLUBLE SALTS OF ALKENE DISULFONATES CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, AND FROM ABOUT 5% TO ABOUT 70% WATER-SOLUBEL SALTS OF HYDROXY DISULFONATES CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, SAID ALKENE DISULFONATES CONTAINING A SULFONATE GROUP ATTACHED TO A TERMINAL CARBON ATOM AND A SECOND SULFONATE GROUP ATTACHED TO AN INTERNAL CARBON ATOM NOT MORE THAN ABOUT SIX CARBON ATOMS REMOVED FROM SAID TERMINAL CARBON ATOM, THE ALKENE DOUBLE BOND BEING DISTRIUBTED BETWEEN THE TERMINAL CARBON ATOM AND ABOUT THE SEVENTH CARBON ATOM, SAID HYDROXY DISULFONATES BEING SATURATED ALIPHATIC COMPOUNDS HAVING A SULFONATE RADICAL ATACHED TO A TERMINAL CARBON, A SECOND SULFONATE GROUP ATACHED TO AN INTERNAL CARBON ATOM NOT MORE THAN ABOUT SIX CARBON ATOMS REMOVED FROM SAID TERMINAL CARBON ATOM, AND A HYDROXY GROUP ATTACHED TO A CARBON ATOM WHICH IS NOT MORE THAN ABOUT FOUR CARBON ATOMS REMOVED FROM THE SITE OF ATTACHMENT OF SAID SECOND SULFONTATE GROUP; (II) FROM ABOUT 5% TO ABOUT 50% OF DETERGENT II WHICH IS AN ALKYL GLYCERYL ETHER SULFONATE DETERGENT HAVING A STRAIGHT CHAIN ALKYL GROUP OF FROM ABOUT 10 TO ABOUT 14 CARBON ATOMS, THE CATION OF SAID SULFONATE BEING SELECTED FROM THE GROUP CONSISTING OF MONOETHANOLAMINE, DIETHANOLAMINE, TRIETHANOLAMINE, AMMONIUM, SODIUM, AND POTASSIUM AND MIXTURES THEREOF; AND (III) FROM ABOUT 5% TO ABOUT 40% OF DETERGENT III WHICH IS A FATTY ACID AMIDE SELECTED FROM THE GROUP CONSISTING OF FATTY ACID MONOETHANOLAMIDE, FATTY ACID MONOISOPROPANOLAMIDE, AN FATTY ACID GLYCERYLAMIDE, THE FATTY ACID GROUPS CONTAINING 10 TO 14 CARBON ATOMS. 